Luminous writing



March 28, 1961 L. T. JENKINS LUMINOUS WRITING Filed Jan. 7, 1957 INVENTOR L/aya 7T JE/zkm:

ATTORNEY LUMINOUS WRITING Lloyd T. Jenkins, Decatur, Ala. (P.0. Box 297, Cary, NC.)

Filed Jan. 7, '1957, Ser. No. 632,898

Claims. (Cl. 252301.3)

The present invention relates to a composition and method for writing in the dark. More particularly, the invention relates to compositions, which when mixed, are capable of generating visible light to provide illumination of a writing outline on a writing surface, or to provide a luminous writing fluid.

The invention also relates to a device for containing and feeding at least one such composition in fluid form into contact with the other to provide continuous visible radiation on a writing surface, which coincides with the writing characters being formed. In addition, the invention is directed to a writing device of the fountain pen type for feeding and bringing into contact the reactive compositions to provide a self-luminous writing outline.

In many instances, it is either desirable or necessary to write in the dark, such as taking notes in conjunction with slide or film presentations in darkened lecture rooms. be necessitated in many circumstances involving military or civilian defensive operations, or military offensive operations. In such cases, only sufiicient illumination to permit following the writing characters is desired to avoid any projection of light.

In the past, there have been many devices suggested for such purpose, all of which require a source ofartificial illumination, such as battery operated incandescent lamps, or fluorescent materials which must be irradiated by ultra violet or other invisible radiation. Battery operated lights are not suitable since they emit too much light, and require dry cell batteries for portability, which are, of course, of limited life. Moreover, in such devices, it is necessary to provide beam-shielding or beamdiffusing elements, and in operations involving blackouts, these devices require extreme precaution in handling due to the danger ofposition exposure.

In the fluorescent devices, activating sources of ultra violet light are required, or in phosphorescent devices previous visible light illumination of the phosphorescent substance involved is necessary in order that the substance will generate visible light in the dark. I

These exists a distinct need for means for Writing in 'the dark which will provide only limited illumination,

light radiation, known as chemiluminescence, to provide illumination of the writing outline on a writing surface, or to provide a luminous writing fluid thus enabling one to write in the dark by following the projected light radiation produced by the chemical reaction.

.It is a further object of the invention to provide a method of writing in the dark utilizing such chemiluminescent materials to provide illumination of the writ- "ing surface and to form luminous writing characters tes Patent Also, writing under blackout conditions may 2,977,320 Patented Mar. 28, 1961 ice the'provision of a fountain pen type device. especially adapted for use with the compositions and method for containing at least one of the reactive components and feeding it into contact or mixing it with a second reactive component to provide chemiluminescence or cold light for writing in the dark. These and other objects and advantages of the invention will be apparent from the following detailed description thereof.

According to the invention a source of limited illumination in the form of visible light suflicient to enable one to write legibly and rapidly in the dark is provided by utilizing a chemical reaction known as chemiluminescence in which certain organic chemical components react with a second chemical component, usually one or more oxidixing agents, to cause light radiation or glowing. These chemicals are reactive in solution with the oxidizing agent, and the resultant reaction temporarily produces a so-called cold or chemiluminescent light. The reactive components are contained separately until the desired time for effecting illumination or providing the luminous writing fluid, and upon bringing the reactive components into contact, the visible light is generated on the writing surface to. permit writing in the dark with facility. 1 The invention contemplates that the reactive components may be contained in a separated condition in a device which feeds the solutions to a common point to provide a continuous light radiation upon contact of the chemicals at the common point. The mixing point is adjacent to or coincident with the writing surface thereby enabling one to write in the dark by following the projected light radiation produced by the chemical reaction. When utilizing the reactive components in separate solution form, a suitable writing device containing two fluid reservoirs may be provided with the reservoirs feeding to a common writing point, so that the components are simultaneously fed and mixed to the writing surface providing a writing fluid for forming writing characters which are self-luminous.

In an alternative embodiment, one of the reactive components, for example, the oxidizing agent, may be incorporated in the material of which the writing surface is composed. The other reactive component is in solution, or other liquid form, suitable for contact with the material of the Writing surface containing the oxiding agent to generate visible light and render the writing characters luminous.

The compositions of the present invention may incorporate any of the several materials which generate visible radiation by chemiluminescence under the influence of an oxidizing agent. Compounds which may be mentioned by way of illustration, and which are particularly adapted for this purpose are 3- and 4-aminophthalhydrazide. Various derivatives of these compounds such as hydroxy and nitro substituted compounds and the acetylated amino compounds mayalso be employed. Various other condensed ring compounds having the chemiluminescent property, such as benzhydrazides, N,N'-dimethyl-biacridyliurndinitrate, and the like ar'e also suitable. The aminophthalhydrazides above m'enor alkali metal'metasilicates' and the like.

tioned are preferred on the basis of their easier preparation and more ready availability, although the invention is in no way limited to these specific compounds.

The other reactive'component is an oxidizing agent or mixture of oxidizing agents which is capable of reacting with the hydrazides or other chemiluminescent material when contacted or admixed therewith in solution form. The: oxidizing agents of the present invention are for the most part those which decompose to generate nascent oxygen among which may be mentioned hydrogenperoxide, perborates, persulfates, perchlonates and hypochlorites. In conjunction with such decomposable oxidizing agents, there may be utilized other mild oxidizing agents which promote the release of free oxygen, such as potassium or sodium ferricyanides and other soluble ferricyanides, soluble copper and cupric ammonium complex salts and the like. The preferred oxidizing agent is hydrogen peroxide used in conjunction with sodium or potassium ferricyanide to accelerate its decomposition upon mixing with the hydrazides or other chemiluminescent substances.

The reaction. to provide the cold or chemiluminescent light is generally carried out in an alkaline medium, al- 7 though certain types of the reactive compounds may involve reaction mechanisms which are not pH sensitive. When utilizing the preferred aminophthalhydrazides of of the invention, an alkaline medium is preferably provided for the reaction by forming an alkaline solution of the hydrazide. The reactive oxidizing component is separately prepared, for example, a hydrogen peroxide solution containing potassium ferricyanide. These twosol'utions constitute the separate reactive components in the two-solution embodiment of the invention, which are stored in separate containers or: reservoirs of a suitable writing device and fed to a common point at the writing surface to provide the luminous writing characters or illumination.

In that alternative of the invention where one reactive component is supplied in fluid form from a writing device andthe other component is incorporated as a layer on the writing surface, such as paper orother suitable material, the writing fluid is preferably a solution of the hydrazide and hydrogen peroxide in dilute alkali solution. The accelerator or other oxidizing agent, such as potassium ferricyam'de, or other hydrogen peroxidedecomposing agent, may be applied to the writing surface as an irnpregnant or coating. When the liquid writingfluid containing the hydrazide and hydrogen peroxide is brought into contact with the paper surface, the reaction generates desired light radiation.

The intensity of the visible radiation and the duration thereof may be controlled by varying'the concentration of thereactive components over a wide range from dilute to saturated solutions; the radiation is increased With increasing alkalinity of'the solution, and the intensity as well as the duration of the visible glow produced by the reaction is decreased with decreasing concentrations ofthe hydrazide or other chemiluminescent material and the oxidizing agent.

In either the two-liquid or one liquid-writing. surface coating embodiments of the invention, the liquid'reactive component may be used with or actually combined with any conventional ink formulation to provide permanent writing visible in daylight or under ordinary illumination. At the same time the necessary'visible radiation is generated by the reactionto permit writing in the dark- The alkalinity of the reaction medium may be provided by. any number of compounds with normally satisfactory results, including caustic soda, sodium carbonate, and hydrolyzable salts providing analkaline pH, suchas trisodium phosphate, and other alkali metal phosphates,

In'so'rne instances, with' suitable accelerators, the reaction medium maybe at a relatively loweripH. For this purpose, organic. ferric chloride complexes may be utilized.

In general, the intensity of q The following serves to illustrate specific formulations that may be utilized according to the invention, although they are not intended as a limitation thereof. Percentages are by weight.

Example I: Two-liquid formulation- (l) (LS-1.0% 3-aminophthalhydrazide in 5-10% sodium hydroxide solution. (2) OS-1.0% hydrogen peroxide in aqueous solution with 0.5-1.0% potassium fer'ricyanide. Example II: One liquid-paper coating formulation- Liquid: (LS-1 .0% 3-aminophthalhydrazide, 0.5-

1.0% hydrogen peroxide in 5-10% sodium hydroxide solution. Paper: Paper'coatedby' dipping in l-2% potassium ferricyanide solution. a

A suitable writing device for feeding and mixing of the reactive components to provide the requisite illumination on the" writing surface, i. e. luminous writing characters, may he any writing pen of the reservoir type. For thetwo-liquid form of the invention the pen is provided with separate reservoirs or chambers, which contain and feed the separated reactive components in solution form to the writing tip of the device In the one liquid-writingniaterial'coating form of the invention; the writing device" may be any conventional type" of pen equipped-with a reservoir for the single liquid containing one of the reactive components in solution form with or withbut ink'added. V

One specific embodiment of asuitable writing device for purposes of the invention shown'in the accompanyingurawin' s, in which Figure 1' isa schematic view of th'e writing device with its asseciated parts,-

Figure 2' is a sectional view taken on'line 22' of Figure l, and p Figure 3 is a sectional" view taken on" line 3- 3 of Figural.

Referringto the drawings, a hollow cylindrical pen barrel'l' is provided at itsupper end with screw threads 2 to which a screw threaded cap 3 is attached. A conical tipj4-is provided at the lower end of the pen'barrel l'with a cylindrical threaded extension 5 which is attaeh'ed't'o the threaded endj 6 of pen barrel 1. providedwith aball' point"! s'eatedin' aperture 8. This ball point! also functionsas a ball'checik for permitting free flowoffluid when the ballis' rolled upon contact with-a writing surface, and which upon cessation ofthe rolling. pressure shutsotf the 'fl'otv" of writingfluid. As shown in all of the figures, the'p'en barreljl" is" provided with a diaphragm or's'eparator 9' vertically" disposed on a" diameter of the" cylindrical barrel 1 and" dividing the interior of the barrel into two chambers; The "separator 9 extends into and divides the conical serew'tip 4 to the ball point'7. A suitable seal 10is provided between the end of the sepai 'a'tof 9 "and the ball point 7. Af flat' disc type seal 11 isfpr'ovide'd between'the screw -ea'pl rand the reservoirs 12 'and'13formedin the pen barrelby'separat'o'r9.

Reservoirs '12 and 13' are" filled separately by unscrewing' the screw cap 3' and adding the solutions of the operation of thedeviee, as abovedes'cribed; is filledwith an alkaline 'soltition" of- 1% by" weight 3 aminophthalhydrazide containing 5% by weight sodium hydroxide.

The conical tip' is Chamber 13 is filled with an aqueous solution containing 1% by weight hydrogen peroxide and 0.5% by weight potassium ferricyanide. Upon feeding and mixing of the reactive solutions in forming writing characters with the ball point pen, a visible light of greenish blue color is generated, permitting one to write by following the projected radiation coinciding with the writing outline.

It may be seen from the above description of the invention that a composition and method for writing in the dark is provided which is not dependent upon artificial light producing devices such as incandescent bulbs, or fluorescent materials which require an activating ultra violet radiation. The simple provision of a two component reactive chemical composition, which components when brought into contact on the Writing surface pro duce cold or chemiluminescent light, facilitates writing in the dark. Thus, legible and rapid writing in the dark is made possible by means of the present invention. In addition, the invention provides a suitable writing device, which is utilized to separately store solutions of the reactive components, and which is adapted to feed the solutions to the writing point of the device to admix the reactive solutions and permit their even and simultaneous flow onto the writing surface to provide the luminous or visible light emanating writing characters. The invention also provides a single liquid containing one of the reactive components with a coating on the writing material surface containing the other reactive component, so that the two are brought into contact to generate the visible light at the point on the writing surface where the writing characters are being formed.

Various modifications and alterations of these specific embodiments above-described may be made without departing from the spirit of the invention, the scope of which is defined by the appended claims. For instance, in utilizing the one liquid-writing surface coating embodiment of the invention, the two chambered writing device may be utilized to contain a single solution of a reactive component in one reservoir and a conventional ink formula in the other reservoir for providing permanency of the writing produced to render the writing characters visible in daylight or under ordinary illumination. Still another modification would be to provide a triple chambered device which may separately contain an ordinary ink formulation, and in the other two chambers the separated solutions containing one each of the reactive components. Alternatively, the ink may be admixed with either of the solutions containing the reactive components provided,

of course, it does not cause decomposition of the reactive components in either of the two solutions.

What I claim is:

1. A method of writing in the dark which comprises, supplying a liquid containing a reactive component which when oxidized produces chemiluminescent light to a writing surface formed on an object from a source dissociated with said object in such manner as to form writing characters on said surface, and contacting said liquid with an oxidizing agent, whereby said liquid and said agent react together to produce visible light coincident with said writing characters.

2. The method according to claim 1 in which the oxidizing agent is contained as a coating on the writing surface and reacts upon contact of the liquid therewith.

3. The method according to claim 1 in which said liquid consists essentially of an alkaline solution of an aminophthalhydrazide, and said oxidizing agent consists essentially of a solution of hydrogen peroxide containing potassium ferricyanide.

4. The method according to claim 1 in which both said liquid and said agent are simultaneously supplied to said surface from separate sources dissociated with said object.

5. The method according to claim 2 in which said liquid consists essentially of a solution of an aminophthalhydrazide, and said oxidizing agent coated on said writing surface consists essentially of an alkali metal ferricyanide.

References Cited in the file of this patent UNITED STATES PATENTS 1,097,981 Krape May 26, 1914 2,302,645 Switzer Nov. 17, 1942 2,420,286 Lacy May 6, 1947 2,505,470 Green Apr. 25, 1950 2,511,369 Petit June 13, 1950 2,550,469 Green Apr. 24, 1951 2,557,563 Reed June 19, 1951 2,647,086 Homer July 28, 1953 2,774,737 Mager Dec. 18, 1956 FOREIGN PATENTS 464,948 Canada May 9, 1950 OTHER REFERENCES Dement: Fluorochemistry Text (1945), Chem. Pub. Co., Brooklyn, N.Y., p. 628. 

1. A METHOD OF WRITING IN THE DARK WHICH COMPRISES, SUPPLYING A LIQUID CONTAINING A REACTIVE COMPONENT WHICH WHEN OXIDIZED PRODUCES CHEMILUMINESCENT LIGHT TO A WRITING SURFACE FORMED ON AN OBJECT FROM A SOURCE DISSOCIATED WITH SAID OBJECT IN SUCH MANNER AS TO FORM WRITING CHARACTERS ON SAID SURFACE, AND CONTACTING SAID LIQUID WITH AN OXIDIZING AGENT, WHEREBY SAID LIQUID AND SAID AGENT REACT TOGETHER TO PRODUCE VISIBLE LIGHT COINCIDENT WITH SAID WRITING CHARACTERS.
 3. THE METHOD ACCORDING TO CLAIM 1 IN WHICH SAID LIQUID CONSISTS ESSENTIALLY OF AN ALKALINE SOLUTION OF AN AMINOPHTHALHYDRAZIDE, AND SAID OXIDIZING AGENT CONSISTS ESSENTIALLY OF A SOLUTION OF HYDROGEN PEROXIDE CONTAINING POTASSIUM FERRICYANIDE. 